High molecular weight resins



United States Patent 3,277,054 HIGH MOLECULAR WEIGHT RESINS Israel J.Dissen, Chicago, D1,, assignor to Velsicol Chemical Corporation,Chicago, Ill., a corporation of Illinois No Drawing. Filed Dec. 6, 1965,Ser. No. 512,032 Claims. (Cl. 260-47) r C1 Cl Structure I wherein R andR are independently selected from the group consisting of hydrogen,halogen, phenyl and lower aliphatic radicals and n is an integer from to1000.

It is preferred for maximizing certain properties of the presentcompositions that n in the above formula be an integer from 50 to 150.

It can be seen from the foregoing formula that due to its symmetry, theR and R substituents are equivalent. Compositions wherein R and R are asfollows are of particular interest.

R1 R2 hydrogen hydrogen halogen hydrogen phenyl lower aliphatic loweraliphatic lower aliphatic halogen halogen methyl hydrogen phenylhydrogen chlorine hydrogen These new resinous compositions can beprepared by contacting phosgene and a compound of the general formula ClOH Cl- -Cl C] R2 Structure H wherein R and R are independently selectedfrom the group consisting of hydrogen, halogen, phenyl, and loweraliphatic radicals, in the presence of an acid acceptor.

The new polymeric compositions obtained by the method of this inventionhave a variety of advantages. These thermoplastic resins have highsoftening points which make them particularly useful in the fabricationof 3,277,054 Patented Oct. 4, 1966 electrical and electronics equipmentand other applications where heat can be generated. As a furtheradvantage in such applications, the new polymeric compositions of thisinvention are non-burning and therefore offer a great safety advantage.

In addition, these new polymeric compositions have unusuallyadvantageous solubility and fusibility not expected on the basis of theliterature. Einhorn (Leibigs Ann. Chem. 300, p. (1898) and subsequentworkers report that the interaction of hydroquinone and phosgene lead toan infusible and insoluble crystalline powder. These compositions aredescribed in the literature as being intractable.

On the contrary, the present polymeric-compositions are soluble andfusible. This enables their ready use in the manufacture of moldedarticles.

Also, the present polymeric compositions exhibit exceptional hydrolyticstability in caustic solutions. This property .is evident at roomtemperature and at elevated temperatures. As to thermal properties, suchas heat distortion temperature and thermal conductivity, the presentcompositions show marked superiority. The electrical resistance of thesecompositions is high and of particular value when used in thepreparation of articles used in the presence of electrical currents.

These properties make the new polymers particularly useful in themanufacture of printed circuit card guides, relay bases, connectors,cover plates, light cell reflector bases, signal light lenses, dials,tuner spacers, telephone line connectors, and other electrical parts.

The monomers having the formula of Structure H are used as the startingmaterials in preparing the new polymers of this invention. Thesemonomers can be prepared, for example, as described in US. Patent2,584,140, granted February 5, 1952, by the rearrangement of Diels-Alder adducts of hexachlorocyclopentadiene and benzo quinones. Thepreparation of such adducts has been described, for example, in US.Patent 2,584,139, granted February 5, 1952. Suitable benzoquinones to beused for the addition reaction to form starting materials useful in thepreparation of the polymers of this invention are therefore 2,3-R R-1,4-benzoquinones in which R and R are independently selected from thegroup consisting of hydrogen, halogen, phenyl, and lower aliphaticradicals. By lower aliphatic radicals are meant those which contain upto four carbon atoms. Typical examples of some suitable benzoquinonesare therefore benzoquinone itself, toluquinone, phenylbenzoquinone,monobromobenzoquinone, dially'lbenzoquinone, 2,3-dichlorobenzoquinone,2,3-dimethylbenzoquinone, ethylbenzoquinone, isopropylbenzoquinone,butylbenzoquinone, and the like.

This method of preparing the present composition comprises contacting acompound of the general formula of Structure II with phosgene in thepresence of an acid acceptor. By acid acceptor, or acid binding agent,is meant a substance which will take up the hydrogen chloride releasedduring the reaction of the Structure 11 with phosgene. One type ofsuitable acid acceptor is an aqueous alkali such as aqueous solutions ofsodium hydroxide, potassium hydroxide, sodium carbonate, potassiumcarbonate, and the like. When such an aqueous alkali is used as the acidacceptor, at least two moles of the alkali 3 should be used for eachmole of Structure II. However, it is advantageous to use an excess ofthe aqueous alkali; and it is therefore preferred to use from aboutthree to about eight moles of alkali for each mole of Structure II. Itis most preferred to use about six moles of alkali for each mole ofStructure I'I.

Another suitable type of acid acceptor is a tertiary amine such aspyridine, triethylamine, tri-n-propylamine, triisoamylamine,dimethylaniline, N,N-dimethyl-p-tolui dine, diethylaniline, and thelike. Such tertiary amines are advantageous acid acceptors for themethod of this invention since they also serve to catalyze the reaction.(Further, many of the amines are also good solvents for the reactantsand the products. Pyridine, for example, can function simultaneously asan acid acceptor, a catalyst, and a solvent, and is therefore apreferred tertiary amine for use in the method of this invention. Thetertiary amines can be used in the same molar proportions as the aqueousalkalies.

'Polymeric compositions of improved molecular weights can 'be obtainedby the use of suitable catalysts in the method of this invention.Although such compositions can be obtained by prolonged reaction timewithout a catalyst, the use of a catalyst is desirable. As was notedabove, the tertiary amines when employed as acid acceptors can alsofunction as catalysts. However, quaternary ammonium bases have beenfound to be good catalysts. Such quaternary ammonium bases are compoundsof the type benzyltrimethylammonium. chloride, benzyltrimethylammoniumhydroxide, (Z-hydroXyethyD-trimethylammonium bicarbonate,hexadecyltrimethylammonium chloride, octadecyltrimethylammoniumchloride, benzyldimethylphenylammonium chloride, 2-dodecylisoquinoliniumbromide, l-hexadecylpyridinium chloride, (2-acetoxypropyl)-trimethylammonium bromide, tetrae-thylammonium chloride,and the like. These quaternary ammonium bases can be used in catalyticquantities. It is preferred to use less than about ten percent by weightof such bases calculated on the weight of Structure 11.

While this method can be carried out in aqueous suspension or in asolvent system which consists entirely of one or more of the tertiaryamine acid acceptors, additional inert solvents can also be used ifdesired. Some typical suitable solvents are dimethylformamide, dioxane,chloroform, tetrahydrofuran, ethylene carbonate, methylene chloride,chlorobenzene, cyclohexanone, and the like.

The temperature at which the method of this invention can be carried outis not critical. The reaction is ordinarily exothermic, and cooling ofthe reaction mixture is desirable to prevent too rapid reaction anddecomposition. Reaction temperatures in the range from about to about 50C. are preferred, and reaction temperatures in the range from about 15to about 35 C. are most preferred. While the reaction is ordinarilycarried out at atmospheric pressure, superatmospheric pressures can alsobe used to facilitate the reaction if desired.

The quantity and the rate of addition of the phosgene are not critical.Ordinarily, the phosgene can be introduced into the reaction mixtureuntil the reaction is no longer exothermic and the mixture becomesviscous. The resulting polymer can then be isolated in several ways. Itcan be precipitated and washed with a nonsolvent such as methanol oracetone. Alternately, the polymer can be taken up in a solvent, and thesolution can be washed thoroughly with water and dried before thesolvent is removed to leave a residue of the polymer.

The manner in which the composition of this invention can be prepared isillustrated in the following examples. Variations in the conditions ofthe resin forming method result in resins with a variety of properties.Unless otherwise noted, temperatures are in degrees centigrade.

4 EXAMPLE 1 Preparation and rearrangement of thebenzoquinonehexachIorocylopentadiene adduct Hexachlorocyclopentadiene (214 g.) was heated slowly with benzoquinone (8 2.6 g.) to a temperatureof about 130-160" and maintained in that temperature range for aboutfifteen minutes. The hot reaction mixture was then poured into a chilledbeaker and quenched with hex EXAMPLE 2 Formation of a resin in thepresence of aqueous alkali and a catalyst A l-liter flask fitted with astirrer, thermometer, gas inlet tube, and condenser was charged with5,8-dihydroxy- 1,2,3,4,9,9 hexachloro 1,4 dihydro 1,4 methanonaphthalene(76.2 g.; 0.2 mole), sodium hydroxide pellets (20.0 g.; 0.5 mole), 3.3ml. of an aqueous 60% benzyltrimethylammonium chloride solution, 330 m1.of distilled water, and 167 ml. of methylene chloride. The mixture wascooled to 20 C., and phosgene was then introduced at the rate of about0.6 g. per minute for 75 minutes, during which time an additional 7 g,of NaOH pellets were added. The Water layer was poured off from thereaction mixture, and the methylene chloride was evaporated on the steambath. The contents of the flask were broken up into small pieces anddried overnight at 90 in a vacuum oven. The dried material, whichweighed 90.7 g., was pulverized, Washed with water, and dried overnightat under vacuum.

EXAMPLE 3 Properties of the resin The dried resinous product prepared inExample 1 was found to be insoluble in methanol and acetone but solublein tetrachloroethylene. melting point of greater than 300. A hot meltfilm prepared from this resin at 600 F. and 5004000 p.s.i was found tohave good flow properties.

EXAMPLE 4 Formation of a resin in the presence of tertiary amine alone5,8 dihydroxy 1,2,3,4,9,9 hexachloro 1,4-dihydro 1,4-methanonaphthalene(41 g.; 0.1075 mole) was dissolved in 225 :ml. of reagent grade pyridinein a 300 ml. flask fitted with a stirrer, thermometer, and condenserwith a CaCl drying tube and constant water flow system.

water with vigorous stirring; and the precipitated polymer was filtered,washed with water, and suspended in l-liter of water at 80 withstirring. The polymer was filtered agam and dried overnight in a vacuumoven at 75.

The dried and powdered product was found to have a softening point of180.

It had a Fisher-Johns.

EXAMPLE 5 EXAMPLE Formation of a resin in the presence of tertiary amineand The rearrangement of the adduct of hexachlorocycloacatalystpentadiene and 2,3-dichlorobenzoquinone yields 5,8-di- A SOO-ml.round-bottomed flask fitted with amechanical 5 g ii octachloro stirrer,reflux condenser, internal thermometer, and gas me anonap a inlet tubewas charged with 5,8-dihydroxy-l,2,3,4,9,9- EXAMPLE 11 hexachloro 14dihydro 14 methanonaphthalene The rearrangement of the adduct ofhexachlorocyclo- (50 0131 11.1016) 42 of Pyndme. 200 of pentadiene and2,3-dimethylbenzoquinone yields 5,8-dimethylene chloride, and 2.5 ml. ofa 40% solution of 10 h d, 6

y roxy ,7 dlmethyl 1,2,3,4,9,9 hexachloro 1,4- benzyltrimethylammonlumhydroxlde in methanol. The

o dihydro 1,4 methanonaphthalene. solution was cooled to and phosgenewas bubbled into the reaction mixture for 7 5 minutes, the temperature 7EXAMPLE 1 being maintained at 30 within 3 by use of a11 e bat-1L Therearrangement of the adduct of hexachlorocyclo- The reaction mixturewasfiltered with suction, and the 15 pentadiene and ethylbenzoquinoneyields 5,8 dihydmXy solid was washed with a little methylene chloride.The 6 ethyl 133,499 hexachloro 1,4 dihydro organic layer was washedtwice with a mixture of 200 methanonaphthalene ml. water and ml.concentrated HCl and dried over anhydrous sodium sulfate. The residueremaining after EXAMPLE 13 evaporation of the solvent on l Steam t Was20 The rearrangement of the adduct of hexachlorocycloat 80 for sevhours, PU1Vel'lZed, al1d dl'led evel'nlght pentadiene andisopropylbenzoquinone yields 5,8-dihyat 80 in a vacuum oven. The driedtan solid had a droxy-6.,i5opropy1.1 2 3 4 9 9 hgx-achloro 4dihYdromeltmg range of 200 230. l,4-met-hanonaphthalene.

A wide variety of other compounds having the general EXAMPLE 14 formulaof Structure II can be contacted with phosgene in the presence of anacid acceptor to produce the new The rearrangement of the adduct ofhexachlorocyclothermoplastic resins of this invention. The followingpentadiene and butylbenzoquinone yields 5,8-dihyd-roxyexamplesillustrate the preparation of suitable starting ma-6-butyl-1,2,3,4,9,9-hexachloro-1,4-dihydro 1,4 methanoterials of theStructure II formula by the general method hth 1 detailed inExarnple 1.Further examples of the resin forming method of this invention aresummarized in the following table. The EXAMPLE 6 reaction of theparticular Structure 11 with phosgene is The rearrangement of the adductof hexachlorocyclof out f the conditions g The q y pentadiene dtoluquinone yields 5,8 dihydroxy-G- acid acceptor is expressed in molesper mole of Structure methyl 1,2,3,4,9,9 hexachloro 1,4 dihydro 1,4- II,Whlle the quantity of catalyst is expressed as thepermethanonaphthalene. cent by Weight of Structure II.

A'dA t CtaltWt. 1%). l l l i (Mo l or per czn) Solvent Temp Example l5 1Aqueous KOH Hexadecyltri- Tetrachloro- (2). methylammoethylene.

chloride 16 1 Aqueous NaOH l-Hexadecylpyri- Methylenechlo- 0 (8). dlinum chloride ride. 17 11 Aqueous NaOH Tetraethylammo- Tetrachloro- 30(6). chloride ethylene.

1s 10 Pyridine (s) Benz yltriinethyl- Pyridine 20 8.111111011111111chloride (5). 19 12 Aqueous sodium Benzyltrimethyl- Methylene chlo- 25carbonate (8). ammonium ride.

chloride (10). 2o 1 Pyridine (6) Pyridine Pyridine- 15 21- 1Triethylamine (3) 'lriethylamine Metiylene chlo- 35 EXAMPLE 7 Theproperties of the self-extinguishing thermoplastic The rearrangement ofthe adduct of hexachlorocycloresms produged by the t of thls Inventionmake them useful in many applications. They can be molded pentadiene andphenylbenzoquinone yields 5,8-d1hydroxy- 6 h 1 12 3 499 hexachloro 1 4dih dr0 1 for example, to give many useful ltems such as cover Egg i yplates, dials, light cell reflector bases, and other parts me ap in theelectrical and electronics industry.

EXAMPLE 8 I claim: The rearrangement of the adduct ofhexachlorocyclopentadiene and monobromobenzoquinone yields 5,8di- 01 C1hydroxy 6 bromo 1,2,3,4,9,9 heXachloro-l,4-dihydro-1,4-methanonaphthalene. C1 C1 C1 EXAMPLE 9 $1 0 The rearrangement of theadduct of hexachlorocyclopentadiene and diallylbenzoquinone yields5,8-dihydroxy- L 1 J 6,7 diallyl 1,2,3,4,9,9 hexac-hloro 1,4dihydro-1,4- R1 R2 11 methanonaphthalene. wherein n is an integer from15 to 1,000; and R and R are independently selected from the groupconsisting of hydrogen, halogen, phenyl and lower aliphatic radicals.

2. Composition of claim '1 wherein n is an integer from 50 to 250.

3. Composition of claim 1 wherein R and R are hydrogen.

4. Composition of claim 1 wherein R is halogen and R is hydrogen.

5. Composition of claim 1 wherein R is phenyl and R is a lower aliphaticradical.

6. Composition of claim 1 wherein R and R are lower aliphatic radicmls.

7. Composition of claim 1 wherein R and R are halogen.

8. Composition of claim 1 wherein R is methyl and 15 R is hydrogen.

8 9. Composition of claim -1 wherein R is phenyl and R is hydrogen.

10. Composition of claim 1 wherein R is chlorine and R is hydrogen.

References Cited by the Examiner UNITED STATES PATENTS 2,584,140 2/1952Segel et al 26062l 2,991,273 7/1961 Hechelhammer et al. 26047 2,997,4598/1961 Schnell et a1 260-47 FOREIGN PATENTS 809,735 3/1959 GreatBritain.

SAMUEL I-I. BLECH, Primary Examiner.

